Hard coat laminated film

Abstract

A first embodiment is a hard coat laminated film which sequentially includes a first hard coat layer and a transparent resin film layer from the surface layer side, and wherein the first hard coat layer is formed from a coating material that contains 100 parts by mass of (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol and 0.01-7 parts by mass of (B) a water repellent agent, while containing no inorganic particles. A second embodiment is a hard coat laminated film which sequentially includes a first hard coat layer and a transparent resin film layer from the surface layer side, and wherein: the first hard coat layer is formed from a coating material that contains (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol and (B) a water repellent agent, while containing no inorganic particles; and the surface of the first hard coat layer exhibits high abrasion resistance (steel wool resistance) as examined by a test under predetermined conditions with use of a JSPS-type tester in accordance with JIS L0849 (2013).

The invention claimed is: 
     
       1. A hard coat laminated film sequentially comprising a first hard coat layer and a transparent resin film layer,
 wherein the first hard coat layer is a cured product of a coating material that contains 100 parts by mass of (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol, and 0.01 to 7 parts by mass of (B) a water repellent agent, the coating material containing no inorganic particles, and 
 (A) the copolymer has a dendrimer structure. 
 
     
     
       2. A hard coat laminated film sequentially comprising a first hard coat layer and a transparent resin film layer,
 wherein the first hard coat layer is a cured product of a coating material that contains (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol, and (B) a water repellent agent, the coating material containing no inorganic particles, 
 (A) the copolymer has a dendrimer structure, and the hard coat laminated film satisfies the following property (i): 
 (i) no scratches are found when the hard coat laminated film is placed on a Gakushin-type tester in accordance with JIS L0849:2013 so that the first hard coat is on the surface side; a steel wool of #0000 is subsequently attached to a rubbing finger of the Gakushin-type tester and a load of 500 g is then applied; and, after 9000 reciprocating rubbings of the surface of the test piece under conditions that the moving speed of the rubbing finger is 300 mm/min and the moving distance is 30 mm, the rubbed portion is visually observed. 
 
     
     
       3. The hard coat laminated film according to  claim 1  sequentially comprising the first hard coat layer, a third hard coat layer, the transparent resin film layer, and a second hard coat layer, wherein the third hard coat layer is a cured product of a coating material containing inorganic particles. 
     
     
       4. The hard coat laminated film according to  claim 1 , wherein a sulfur content in (A) the copolymer is 0.1 to 12% by mass. 
     
     
       5. The hard coat laminated film according to  claim 1 , wherein a mass average molecular weight of (A) the copolymer in terms of polystyrene determined from a differential molecular weight distribution curve measured by gel permeation chromatography using tetrahydrofuran as a mobile phase is 5,000 to 200,000. 
     
     
       6. The hard coat laminated film according to  claim 1 , wherein (B) the water repellent agent contains a (meth)acryloyl group-containing fluorine-based water repellent agent. 
     
     
       7. An article comprising the hard coat laminated film according to  claim 1 . 
     
     
       8. The hard coat laminated film according to  claim 2  sequentially comprising the first hard coat layer, a third hard coat layer, the transparent resin film layer, and a second hard coat layer, wherein the third hard coat layer is a cured product of a coating material containing inorganic particles. 
     
     
       9. The hard coat laminated film according to  claim 2 , wherein a sulfur content in (A) the copolymer is 0.1 to 12% by mass. 
     
     
       10. The hard coat laminated film according to  claim 2 , wherein a mass average molecular weight of (A) the copolymer in terms of polystyrene determined from a differential molecular weight distribution curve measured by gel permeation chromatography using tetrahydrofuran as a mobile phase is 5,000 to 200,000. 
     
     
       11. The hard coat laminated film according to  claim 2 , wherein (B) the water repellent agent contains a (meth)acryloyl group-containing fluorine-based water repellent agent. 
     
     
       12. An article comprising the hard coat laminated film according to  claim 2 . 
     
     
       13. The hard coat laminated film according to  claim 1 , wherein the hard coat laminated film sequentially comprises the first hard coat layer, the transparent resin film layer, and a second hard coat layer, wherein the second hard coat layer is a cured product of a coating material containing 100 parts by mass of (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol, and 0.01 to 10 parts by mass of (C) a leveling agent. 
     
     
       14. The hard coat laminated film according to  claim 2 , wherein the hard coat laminated film sequentially comprises the first hard coat layer, the transparent resin film layer, and a second hard coat layer, wherein the second hard coat layer is a cured product of a coating material containing (A) a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol, and (C) a leveling agent. 
     
     
       15. The hard coat laminated film according to  claim 1 , wherein the hard coat laminated film satisfies the following property (i):
 (i) no scratches are found when the hard coat laminated film is placed on a Gakushin-type tester in accordance with JIS L0849:2013 so that the first hard coat is on the surface side; a steel wool of #0000 is subsequently attached to a rubbing finger of the Gakushin-type tester and a load of 500 g is then applied; and, after 9000 reciprocating rubbings of the surface of the test piece under conditions that the moving speed of the rubbing finger is 300 mm/min and the moving distance is 30 mm, the rubbed portion is visually observed. 
 
     
     
       16. The hard coat laminated film according to  claim 1 ,
 wherein (a1) the polyfunctional (meth)acrylate comprises (a1-1) a polyfunctional (meth)acrylate, 
 the number of (meth)acryloyl groups in one molecule of (a1-1) the polyfunctional (meth)acrylate is 3 or more, and 
 (a2) the polyfunctional thiol comprises (a2-1) a polyfunctional thiol, 
 the number of thiol groups in one molecule of (a2-1) the polyfunctional thiol is 3 or more. 
 
     
     
       17. The hard coat laminated film according to  claim 2 ,
 wherein (a1) the polyfunctional (meth)acrylate comprises (a1-1) a polyfunctional (meth)acrylate, 
 the number of (meth)acryloyl groups in one molecule of (a1-1) the polyfunctional (meth)acrylate is 3 or more, and 
 (a2) the polyfunctional thiol comprises (a2-1) a polyfunctional thiol, 
 the number of thiol groups in one molecule of (a2-1) the polyfunctional thiol is 3 or more.